Thermosetting resin composition containing a polyphenylene ether and a brominated fire retardant compound

ABSTRACT

A resin composition for use in making pre-pregs and structural laminates contains a curable composition comprising:
         a functionalized poly(phenylene ether) having the structure:       

     
       
         
         
             
             
         
       
         
         
           
             a radical initiator; 
             an unsaturated monomer; and 
             a flame retardant comprising the compound 1,1′(ethane-1,2-diyl)bis[pentabromobenzene], 
             wherein Y, m and n are defined herein.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Ser. No. 61/601,483, filed Feb. 21, 2012, the disclosure of which is incorporated herein by reference in its entirety.

FIELD OF THE INVENTION

The present invention generally relates to a curable resin composition, a cured resin composition, a sheet-like cured resin, a laminated body, a prepreg, electronic parts, single and multilayer circuit boards comprising a poly(phenylene ether) resin composition, for use, e.g., in single and multilayer printed circuit boards.

SUMMARY OF THE INVENTION

The novel curable compositions of the present invention include:

A curable composition comprising:

a functionalized poly(phenylene ether) having the structure:

a radical initiator;

an unsaturated monomer; and

a flame retardant comprising the compound 1,1′(ethane-1,2-diyl)bis[pentabromobenzene],

wherein Y, m and n are defined herein.

Other embodiments of the present invention are a cured resin, a sheet-like cured resin, a laminated body, a prepreg, electronic parts, and single and multilayer circuit boards comprising the novel curable compositions of the present invention.

DETAILED DESCRIPTION OF THE INVENTION

Curable compositions including functionalized poly(phenylene ether) and copolymerizable monomer compositions are known for a wide variety of thermoset applications. However, there is an ongoing need for formulations that achieve a balance of properties useful for thermoset compositions.

The present invention provides curable compositions useful for the preparation of prepregs and laminates exhibiting desirable characteristics such as high interlaminar bond strength, robust thermal stability, good process ability, good moisture resistance, excellent dielectric properties, very low thermal expansion, and high reliability. These compositions are useful for various applications, including the preparation of single and multilayer printed circuit boards.

In one embodiment, the invention provides a curable composition comprising a functionalized poly(phenylene ether) resin. As used herein, a “functionalized” poly(phenylene ether) is a poly(phenylene ether) that is “capped,” having a polymerizable carbon-carbon double bond at each end of the molecule. One method of preparing such molecules is to first prepare a poly(phenylene ether) having a hydroxy group at each end of the molecule (e.g., a “dihydroxy poly(phenylene ether)”), then react the dihydroxy poly(phenylene ether) with sufficient capping reagent to form polymerizable capping groups at each end of the molecule.

For example in one embodiment, a functionalized poly(phenylene ether) of the invention has the structure:

wherein m and n are independently 1 to 500; and Y is absent or has the structure:

where R₁ and R₂ are each independently hydrogen or C₁-C₁₂ alkyl, or the like.

In one preferred embodiment of the invention, m and n independently represent integers in the range of 1 to 100. In another preferred embodiment m an n represent integers in the range of 1 to 50. In another preferred embodiment, Y is absent. In yet another preferred embodiment, Y is an isopropylidene group. In another preferred embodiment, the poly(phenylene ether) is MX9000-111 (Sabic).

The curable composition may comprise about 10 to about 50 parts by weight of the functionalized poly(phenylene ether). Within this range, the amount of the functionalized poly(phenylene ether) may be about 15, 20, 25, 30, 35 or about 40 parts by weight of the curable composition. In one embodiment, the functionalized poly(phenylene ether) polymer is present in the composition in an amount of about 30 to 60 percent by weight. In another embodiment, the poly(phenylene ether) is present in an amount of 30 to 50 percent by weight. In another embodiment, the poly(phenylene ether) is present in an amount of about 40 percent by weight. In yet another embodiment of the invention, the functionalized poly(phenylene ether) is present in the composition at about 37 parts by weight of the total composition.

In addition to the functionalized poly(phenyl ether), the curable composition is combined with a flame retardant. Flame retardant compounds useful in this invention include, e.g., halogenated flame retardants, more specifically, brominated flame retardants. Brominated flame retardants of the invention may comprise the compound 1,1′(ethane-1,2-diyl)bis[pentabromobenzene], and derivatives thereof. An example of a preferred flame retardant of the invention is the commercial product Saytex® 8010 (Albemarle®). The flame retardant is advantageously present in an amount within the range of about 5 to about 60 parts by weight per 100 parts by weight of the total composition. In one embodiment of the invention, the flame retardant is present in an amount of about 10 to about 60 percent by weight. In another embodiment, the flame retardant is present in an amount of 10 to about 30 parts by weight. In another embodiment, the flame retardant is present in an amount of about 10 to about 20 percent by weight. In another embodiment, the flame retardant is present in an amount of about 20 percent by weight. In a preferred embodiment, the flame retardant is present in an amount of about 18 parts per weight of the total composition.

The curable composition may also comprise an unsaturated monomer. As used herein, the term “unsaturated monomer” is a polymerizable monomer comprising a carbon-carbon double bond. In one embodiment of the invention, the unsaturated monomer is a mono- or poly-functional acrylate or methacrylate ester. In this embodiment, the unsaturated monomer may comprise bisphenol A diacrylate or dimethacrylate, ethoxylated bisphenol A diacrylate, available as the commercial product SR-349 (Sartomer), ethoxylated bisphenol A dimethacrylate, available as the commercial product SR-348 (Sartomer) and trimethylolpropane trimethacrylate, available as the commercial product SR-350 (Sartomer). In another embodiment, the unsaturated monomer is a bismaleimide (e.g., MDA-BMI, TDA-BMA).

In another preferred embodiment of the invention, the unsaturated monomer is an allylic monomer. An allylic monomer includes any organic compound comprising at least one allyl (—CH₂—CH═CH₂) group. In one embodiment, the allylic monomer comprises at least two allyl groups. In another embodiment, the allylic monomer comprises at least three allyl groups. Suitable allylic monomers of the invention include, e.g., diallylphthalate, diallylisophthalate, triallylmellitate, triallylmesate, triallyl benzenes, triallylcyanurate, triallylisocyanurate, mixtures thereof, partial polymerization products prepared therefrom, and the like. In one preferred embodiment of the invention, the allylic monomer is triallylisocyanurate.

The composition may generally comprise about 1 to about 60 parts by weight of the unsaturated monomer per 100 parts by weight total of the curable composition. In one embodiment of the invention, the unsaturated monomer is present in the composition in an amount of about 10 to 40 parts by weight. In another embodiment, the unsaturated monomer is present in an amount of about 15 to 25 parts by weight. Within this range, the unsaturated monomer amount may specifically be at least about 5, 10, 15, 16, 17, 18, 19, 20 or about 25 parts by weight of the total composition. In a preferred embodiment, the monomer comprises 19 parts by weight of the total composition.

The curable composition may, optionally, further comprise a catalyst to, e.g., initiate the polymerization, curing or crosslinking of the components of the composition. The catalyst may include any compound capable of producing free radicals at elevated temperatures. Such catalysts may include both peroxy and non-peroxy based radical initiators. Examples of useful peroxy initiators include, for example, benzoyl peroxide, dicumyl peroxide, methyl ethyl ketone peroxide, lauryl peroxide, cyclohexanone peroxide, t-butyl hydroperoxide, t-butyl benzene hydroperoxide, t-butyl peroctoate, 2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl-2,5-di(t-butylperoxy)-hex-3-yne, di-t-butylperoxide, t-butylcumyl peroxide, α,α′-bis(t-butylperoxy-m-isopropyl)benzene, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, di(t-butylperoxy) isophthalate, t-butylperoxy benzoate, 2,2-bis(t-butylperoxy)butane, 2,2-bis(t-butylperoxy)octane, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, di(trimethylsilyl)peroxide, trimethylsilylphenyltriphenylsilyl peroxide, and the like, and mixtures thereof. Suitable non-peroxy initiators include, for example, 2,3-dimethyl-2,3-diphenylbutane, 2,3-trimethylsilyloxy-2,3-diphenylbutane, and the like, and mixtures thereof. In one embodiment of the invention, the catalyst is a peroxy catalyst. In another preferred embodiment, the catalyst is 2,5-dimethylhexane-2,5-dihydroperoxide. In another preferred embodiment, the catalyst is 2,5-dimethyl2,5-di(t-butypperoxy)-hex-3-yne, available as the commercial product DYBP (United Initiators). In another preferred embodiment, the catalyst is 45% 2,5-dimethyl-2,5-di(t-butylperoxy)-hex-3-yne which is dispersed onto a calcium carbonate and silica mixture, available as the commercial product DYBP-45-IC2 (United Initiators). In another preferred embodiment, the catalyst is 2,5-dimethyl-2,5-di(t-butylperoxy)-hexane, available as the commercial product DHBP (United Initiators).

The catalysts and/or initiators may be used in their pure form or in a mixture with carrier compounds, such as calcium carbonate, calcium sulfate, or silica. The concentration of the initiators in the mixture can range from 10 to 90 percent by weight.

The catalyst may be used in the composition at about 0 to about 10 parts by weight per 100 parts by weight of the total composition. In one embodiment of the invention, the catalyst is present in an amount of about 0 to about 4 percent by weight. In another embodiment, the catalyst is present in an amount of about 0 to 2 percent by weight. Within this range, the catalyst amount may be at least about 0.2 part by weight, more specifically at least about 1 part by weight. Also within this range, the catalyst amount may be about 0.3, 0.4, 0.5, 0.6, 0.65, 0.7, 0.75, 0.8, 0.9, up to about 3 parts by weight. In a preferred embodiment 0.75 parts by weight of the total composition comprises a catalyst.

The curable composition may further comprise one or more fillers. Examples of such fillers are well known in the art. Non-limiting examples of fillers include silica powder, such as fused silica and crystalline silica, boron-nitride, alumina, and magnesium oxide (or magnesia). Other fillers of the invention include calcium sulfate, calcium carbonate, talc, glass spheres, kaolin, clay, mica, silicate spheres, cenospheres, aluminosilicate, sand, quartz, quartzite, perlite, and synthetic silica, including those with various silane coatings, and the like. The fillers may be present in the composition at a range of about 1 to about 50 parts by weight per 100 parts by weight of the total composition. For example, in one embodiment of the invention, the filler is present in an amount of about 10 to about 40 parts by weight. In another embodiment, the filler is present in an amount of about 15 to about 35 parts by weight. In one preferred embodiment, the filler is present at 25 parts by weight.

The composition may also contain adhesion promoters to improve adhesion of the thermosetting resin to the filler or to an external coating or substrate. Adhesion promoters include chromium complexes, silanes, titanates, zirco-aluminates, propylene maleic anhydride copolymers, reactive cellulose esters and the like. The adhesion promoter may be included in the thermosetting resin itself, or coated onto any of the fillers described above to improve adhesion between the filler and the thermosetting resin. For example such promoters may be used to coat a silicate fiber or filler to improve adhesion of the resin matrix. The adhesion promoter may be present in the composition in an amount of 0 to 1 parts by weight of the total composition. In one embodiment of the invention, the adhesion promoter is present in an amount of about 0.05 to about 0.5 parts by weight. In another embodiment of the invention, the adhesion promoter is present in an amount of about 0.1 to about 0.3 part by weight. In another embodiment, the adhesion promoter is present in an amount of 0.1, 0.2, 0.25, 0.3, 0.4, 0.5 parts by weight of the composition. In a preferred embodiment, the adhesion promoter is present in an amount of about 0.25 parts by weight.

The compositions of the invention may be dissolved in an effective amount of an inert solvent. Suitable solvents include solvents that are capable of being removed by means such as evaporation. Solvents such as methyl ethyl ketone and cyclohexanone are preferred. Solvents of the invention also include hydrocarbon type solvents such as toluene and xylene. Other ketone-type solvents such as methyl methyl isobutyl ketone, and cyclopentanone are also useful.

The poly(phenylene ether) composition may, optionally, further comprise one or more additives known in the art such as, e.g., dyes, pigments, colorants, antioxidant, heat stabilizers, ion scavengers, adhesion promoters, plasticizers, lubricants, flow modifiers, antiblocking agents, and the like, and combinations thereof. Those skilled in the art may select suitable additives and determine suitable amounts of the additive reagent without undue experimentation.

In some embodiments of the invention, a method is provided for forming the curable composition, by blending a poly(phenylene ether) and any of the above-described components of the composition at a temperature in the range of 10 to 50° C. to provide a blend. Another embodiment is a cured composition obtained by curing any of the above-described curable compositions. It will be understood that the term “curing” includes partially curing and fully curing. Because the components of the curable composition may react with each other during curing, the cured compositions may be described as comprising the reaction products of the curable composition components. The curable compositions of the present invention are typically cured at a temperature of between about 150 and 250° C. For example, in one embodiment of the invention, the curable compositions of the invention are cured at a temperature of 160 to 230° C. In another embodiment, the composition is cured at a temperature of about 175 to about 220° C. In another embodiment, the composition is cured at a temperature of 216° C. A preferred curing temperature is from 190 to about 220° C.

In some embodiments, the invention further pertains to prepregs for use in the electronics industry incorporating the curable compositions of the present invention. Prepregs for use in the electronics industry (particularly for printed wiring or circuit boards) are generally produced by impregnating a supporting or reinforcing material (usually based on glass fibers, either as a woven or nonwoven fabric or in the form of a cross-ply laminate of unidirectionally oriented parallel filaments) with a curable composition, followed by the curable composition being cured wholly or in part. The latter process is the most common one, and a fabric impregnated with a partially cured resin is usually referred to as a “prepreg.” To make a printed wiring board from a prepreg fabric one or more layers of the prepreg are laminated with, for example, one or more layers of copper.

As the base material of woven fabric or non-woven fabric used in the prepreg of the present invention, there may be used natural fiber base materials such as paper or cotton linter; organic synthetic fiber base materials such as Aramid, polyvinyl alcohol, polyester or acrylic fiber, and inorganic fiber base materials such as glass and asbestos. A glass fiber base material is preferable from the viewpoint of flame resistance. Examples of the glass fiber base materials include, but are not limited to, woven fabric using E glass, NE glass (from Nittobo, Japan), C glass, D glass, S glass or Quartz glass, glass non-woven fabric in which short fibers are adhered into a sheet-like material with an organic binder, and further those in which glass fiber and other fiber types are mixed and made fabric.

According to the present invention, a prepreg can be produced by impregnating the above varnish into a base material such as a woven fabric or non-woven fabric followed by drying. The resulting prepreg may be laminated with one or more layers as necessary to make a composite structure, and after application of a metal foil such as copper foil or aluminum foil to both surfaces of the structure, may be subjected to pressurization and hot pressing to obtain a metal clad laminated board.

According to the present invention, a printed circuit or wiring board can be obtained by performing circuit processing on the metal foil of the metal foil clad laminated board. Circuit processing can be carried out by, for example, forming a resist pattern on the surface of the metal foil, removing unnecessary portions of the foil by etching, removing the resist pattern, forming the required through holes by drilling, again forming the resist pattern, plating to connect the through holes, and finally removing the resist pattern. A multi-layer printed circuit or wiring board can be obtained by additionally laminating the above metal foil clad laminated board on the surface of the printed wiring board obtained in the above manner under the same conditions as described above, followed by performing circuit processing in the same manner as described above. In this case, it is not always necessary to form through holes, and via holes may be formed in their place, or both may be formed. These laminated boards are then laminated the required number of times.

The printed circuit or wiring board produced in the above manner can be laminated with metal foil provided with adhesive on one surface or both surfaces in the form of an inner layer circuit board. This lamination molding is normally performed under heating and pressurization. Examples of metal foil include copper foil and aluminum foil. A multi-layer printed circuit board can then be obtained by performing circuit processing in the same manner as described above on the resulting metal foil clad laminated board.

The formulation of the present invention is also compatible with electroless nickel immersion gold (ENIG) applications. Electrolesss nickel immersion gold is a type of surface plating used for printed circuit boards, consisting of electroless nickel plating covered with a thin layer of immersion gold which protects the nickel from oxidation. Electroless nickel immersion gold surface plating provides improved hardness, wear resistance, corrosion resistance, minimal magnetic properties and high deposit uniformity.

The invention is further illustrated by the following non-limiting examples.

EXAMPLE 1

A curable composition of the invention was prepared by dissolving poly(phenylene ether) resin MX9000-111 (37 Ibs) (Sabic), triallylisocyanurate (DIAK#7; DuPont) (19 Ibs), 2,5-dimethyl-2,5-di(tertbutylperoxy)-hex-3-yne (0.75 Ibs) (DYBP United Initiators) and OFS-6030 (0.25 Ibs) (Xiameter) in a solvent solution containing methyl ethyl ketone (44.50 Ibs) and cyclohexanone (14.50 Ibs). 1,1′(ethane-1,2-diyl)bis[pentabromobenzene]resin Saytex 8010 (18 Ibs) and silica filler SC-2500-SEJ (25 Ibs) (Admatechs, Japan) was added and dispersed into the resin solution using high shear mixing under ambient conditions.

The curable composition prepared in this example exhibited improved properties when tested using standard Interconnect Stress Testing (IST) and Conductive Anodic Filament (CAF) Test procedures.

The IST testing was done using GT40800D (PWB Interconnect Solutions) coupons prepared using the curable composition described above. The coupon was prepared using a 20 layer design with a 0.120″ overall thickness. The coupon was preconditioned at 260° C. 6 times before testing. Each testing cycle was conducted at a temperature of 25 to 150° C. The coupon passed 1000 test cycles.

CAF tests were conducted using coupons prepared using the curable composition described above. In the CAF tests, the coupons were constructed as 26-layer boards with a 0.130″ thickness, using 1035, 1080, 3313, and 2116 glass with H/H and 1 1 oz innerlayer. The coupon was 4″×7.1″ in size. The coupon technology consisted of a quad array containing a 0.8 mm pitch/0.010″ drill; 0.8 mm pitch/0.012″ drill; 1.0 mm pitch/0.010″ drill; and 1.0 mm pitch/0.012″ drill; with 13,400 total drilled holes per array (˜3,350 opportunities for each technology pair). The coupons were reflowed 6×260° C. before testing. The samples were then tested at 50° C./80% RH/15V Bias for 600 hours with an initial 96 hour stabilization period. 100% of the samples tested passed CAF testing.

COMPARATIVE EXAMPLES 1-3

Three comparison samples were formulated as described in Example 1. However, in the comparative samples, Saytex 8010 was replaced with BC-58™ (Great Lakes Chemical Corporation), Exolit OP 930® (Clariant), or Saytex® BT-93 (Albemarle Corporation), as shown in Table 1. BC-58™ is a brominated, aromatic flame retardant. Exolit OP930® is a fine-grained powder flame retardant based on an organic phsphinate. Saytex® BT-93 is a brominated flame retardant of the structure ethylene-1,2-bis(tetrabromophthalimide). Laminate testing was performed according to IPC 4101 industry standard methods. Pressure cooker solder dip testing was performed using standard methods. In particular, for pressure cooker solder dip studies, samples were placed in a pressure cooker apparatus and heated under elevated pressure (15 psi). Samples were then placed in molten solder and time to failure values were evaluated.

The properties of the resulting laminates are shown in Table 1. AB conditioning values in Table 1 represent Dk or Df values after the test specimen is dried. The IPC values in Table 1 represent data generated after the specimen is dried and then conditioned for 24 hours at room temperature at 50% RH.

TABLE 1 Test Example 1 Comp. Ex. 1 Comp. Ex. 2 Comp. Ex. 3 Description Parameters (Saytex 8010) BC-58 OP 930 BT-93 Press Cycle Cure temp, 30/350/3+60/ 30/350/3+60/ 30/350/3+60/ 30/350/3+60/ ° F./dwell time, 420/6° F./250 psi 420/3/300 psi 420/3/200 psi 420/3/250 psi min/heat up rate ° F./min/pressure Dk/Df @ 10 Dk AB:3.88 AB:3.80 AB:3.67 AB:3.83 GHz [Split Post IPC: 3.89 IPC: 3.81 IPC: 3.72 IPC: 3.88 Cavity Method Df AB: 0.0051 AB: 0.0052 AB: 0.0047 AB: 0.0048 2-2116] IPC: 0.0059 IPC: 0.0060 IPC: 0.0056 IPC: 0.0060 Resin content 60.2% 58.6% 57.6% 58.2% DMA Tg (° C.) E′/E″/TanDelta 236/260/ 206/233/239 224/255/ 226/255/262 267 /260 TMA(° C.) Tg° C. 233 198 222 228 8-7628 Alpha 1 Z-CTE 40 44 39 40 (50° C. to Tg −5° C.) Alpha 2 Z-CTE 220 261 230 229 (Tg +5° C. to 260° C.) Overall Z-CTE 1.5% 2.4% 1.9% 1.6% (50° C. to 260° C.) T-288 Time to failure >120 13 >120 >120 (minutes) T-300 Time to failure >120 3 >120 >120 (minutes) Copper Peel WG lbs/in 6.09 lost in etcher 3.34 7.02 Test machine 8-7628(Ib/in) XG lbs/in 6.23 5.71 4.4 6.53 Interlaminar WG lbs/in 4.79 5.72 2.32 1.38 Bond Strength XG lbs/in 5.28 6.5 2.91 2.28 2-7628 (Ib/in) Pressure Cooker Time to failure >600 >600 450 >600 Solder Dip (seconds) (PCSD) 550° F. % wt gain 0.18% 0.15% 0.22% 0.16% Range (seconds) all >600 all >600 600/150/600 all >600 4″X4″ SOLDER Average of 3 >600 339 >600 >600 FLOAT Samples (seconds) BLISTER Flammability Total burn time (5 10 11 11 10 (UL94) samples) (seconds) UL94 rating V-0 V-0 V-0 V-0

The above tabulated data reveals that laminates prepared with the curable composition of the present invention, as shown in Example 1, have overall improved properties including, for example, a high interlaminar bond strength, high thermal stability, and high Tg values. Such properties are of importance for printed circuit board applications.

COMPARATIVE EXAMPLES 4-6

Three comparison samples were formulated as described in Example 1. However, in the comparative samples, Saytex 8010 was replaced with PX-200 (Daihachi Chemical Industry Co.), BR-30 (Kowa), or DER560 (Dow), as shown in Table 2. PX-200 is a condensed phosphate ester-based flame retardant. BR-30 is a brominated flame retardant comprising the compound tribromophenyl acrylate. DER560 is a brominated diglycidyl ether of bisphenol-A. Laminate testing was performed according to IPC 4101 industry standard methods. Pressure cooker solder dip testing was performed using standard methods. In particular, for pressure cooker solder dip studies, samples were placed in a pressure cooker apparatus and heated under elevated pressure (15 psi). Samples were then placed in molten solder and time to failure values were evaluated.

The properties of the resulting laminates are shown in Table 2. AB conditioning values in Table 2 represent Dk or Df values after the test specimen is dried. The IPC values in Table 2 represent data generated after the specimen is dried and then conditioned for 24 hours at room temperature at 50% RH.

TABLE 2 Test Example 1 Comp. Ex. 4 Comp. Ex. 5 Comp. Ex. 6 Description Parameters (Saytex 8010) PX-200 BR-30 DER560 Press Cycle Cure temp, ° F. 30/350/3+ 30/350/3+60/ 30/350/3+60/420/3/ 30/350/3+60/420 /dwell time, 60/420/6/ 420/6/250 psi 200 PSI /3/200 PSI min/ heat up 250 psi rate, ° F./min, /pressure Dk/Df @10 Dk 3.89 4.01 3.92 3.95 GHz Df 0.0059 0.0052 0.0051 0.0138 [Split Post Resin 60.2% 49.6% 57.4% 56.4% Cavity Content method], 2-2116 DMA Tg ,° C. E′/E″/Tan- 236/260/267 131/166/184 213/229/235 170/194/202 Delta TMA(° C.) Tg° C. 233 131 210 145 8-7628 Alpha 1 Z- 40 79 43 46 CTE (50° C. to Tg - 5° C.) Alpha 2 Z- 220 304 253 222 CTE (Tg +5° C. to 260° C.) Overall Z- 1.5% 4.5% 2.1% 3.0% CTE (50° C. to 260° C.) T-288 Time to >120 n/a 35 42 failure (minutes) T-300 Time to >120 >120 16 13 failure (minutes) Copper Peel WG lbs/in 6.09 6.44 9.48 9.12 Strength, lb/in XG lbs/in 6.23 6.08 9.09 8.63 8-7628 Interlaminar WG lbs/in 4.79 7.24 6.08 4.37 Bond XG lbs/in 5.28 8.97 7.01 5.54 Strength 2-7628(Ib/in) Pressure Average of 3 >600 >600 >600 >600 Cooker Samples Solder Dip (seconds) 8-7628 % wt gain 0.18% 0.12% 0.11% 0.32% [etched] Range all >600 all >600 all >600 all >600 SOLDER Average of 3 >600 >600 >600 >600 FLOAT Samples BLISTER (seconds) Flammability Total burn 10 182 10 14 (UL94) time (5 samples) (seconds) UL94 rating V-0 FAIL V-0 V-0

The above tabulated data reveals that laminates prepared with the curable composition of the present invention, as shown in Example 1, have overall improved properties including, for example, a high interlaminar bond strength, high thermal stability, and high Tg values. These properties are of importance for manufacture of pre-pregs, laminate structures, and for pre-pregs that are for use in printed circuit board applications.

As is well known to those of ordinary skill in the art, formulations having excellent properties over a range of parameters are highly desirable. It is also known in the art that it is relatively easy to improve one property in a formulation but getting a product having desirable properties across a range of different parameters is difficult to achieve. Therefore, the compositions of the present invention, which offer general improvements over several parameters, including high interlaminar bond strength, high thermal stability, and high Tg values, represent a marked improvement over prior compositions. 

The invention claimed is:
 1. A curable composition, comprising: a functionalized poly(phenylene ether) having the structure:

a radical initiator; an unsaturated monomer; and a flame retardant comprising 1,1′(ethane-1,2-diyl)bis[pentabromobenzene], wherein Y is absent or has the structure:

where R₁ and R₂ are each independently hydrogen or C₁-C₁₂ alkyl, and m and n are independently 1 to about
 100. 2. The composition of claim 1, wherein the unsaturated monomer comprises triallyl isocyanurate.
 3. The composition of claim 1, wherein the composition comprises from about 10% to about 40% by weight of the unsaturated monomer.
 4. The composition of claim 3, wherein the composition comprises from about 15% to about 25% by weight of the unsaturated monomer.
 5. The composition of claim 1, wherein the radical initiator comprises 2,5-dimethyl-2,5-di(t-butylperoxy)-hex-3-yne.
 6. The composition of claim 5, wherein the radical initiator further comprises dicumyl peroxide.
 7. The composition of claim 1, wherein the composition comprises from about 0.2% to about 3% by weight of the radical initiator.
 8. The composition of claim 7, wherein the composition comprises from about 0.2% to about 2% by weight of the radical initiator.
 9. The composition of claim 1, further comprising a silica filler.
 10. The composition of claim 9, wherein the composition comprises from about 1% to about 50% by weight of the silica filler.
 11. The composition of claim 10, wherein the composition comprises from about 10% to about 40% by weight of the silica filler.
 12. The composition of claim 1, further comprising an adhesion promoter, the adhesion promoter comprising a silane.
 13. The composition of claim 12, wherein the composition comprises from about 0.05% to about 1% by weight of the adhesion promoter.
 14. The composition of claim 13, wherein the composition comprises from about 0.1% to about 0.3% by weight of the adhesion promoter.
 15. The composition of claim 1, wherein Y is absent.
 16. The composition of claim 1, wherein the composition comprises from about 10% to about 50% of the poly(phenylene ether).
 17. The composition of claim 16, wherein the composition comprises from about 20% to about 40% of the poly(phenylene ether).
 18. The composition of claim 1, wherein the composition comprises from about 10% to about 60% by weight of the flame retardant.
 19. The composition of claim 18, wherein the composition comprises from about 10% to about 20% by weight of the flame retardant.
 20. A curable composition, comprising: a functional poly(phenylene ether) having the structure:

a flame retardant comprising 1,1′(ethane-1,2-diyl)bis[pentabromobenzene]; a radical initiator comprising 2,5-dimethyl-2,5-di(t-butylperoxy)-hex-3-yne; an unsaturated polymer comprising triallyl isocyanurate; a silica filler; and an adhesion promoter comprising a silane, wherein Y is absent or has the structure:

where R₁ and R₂ are each independently hydrogen or C₁-C₁₂ alkyl and m and n are independently 1 to about
 100. 21. The composition of claim 20, wherein the composition comprises from about 10% to about 50% of the poly(phenylene ether).
 22. The composition of claim 21, wherein the composition comprises from about 20% to about 40% of the poly(phenylene ether).
 23. The composition of claim 20, wherein the composition comprises from about 10% to about 60% by weight of the flame retardant.
 24. The composition of claim 23, wherein the composition comprises from about 10% to about 20% by weight of the flame retardant.
 25. The composition of claim 20, wherein the radical initiator further comprises dicumyl peroxide.
 26. The composition of claim 20, wherein the composition comprises from about 0.2% to about 3% by weight of the radical initiator.
 27. The composition of claim 26, wherein the composition comprises from about 0.2% to about 2% by weight of the radical initiator.
 28. The composition of claim 20, wherein the composition comprises from about 10% to about 40% by weight of the unsaturated monomer.
 29. The composition of claim 28, wherein the composition comprises from about 15% to about 25% by weight of the unsaturated monomer.
 30. The composition of claim 20, wherein the composition comprises from about 1% to about 50% by weight of the silica filler.
 31. The composition of claim 30, wherein the composition comprises from about 10% to about 40% by weight of the silica filler.
 32. The composition of claim 20, wherein the composition comprises from about 0.05% to about 1% by weight of the adhesion promoter.
 33. The composition of claim 32, wherein the composition comprises from about 0.1% to about 0.3% by weight of the adhesion promoter.
 34. A woven or non-woven fabric impregnated with the composition of claim
 20. 35. A laminate, comprising at least one layer of the fabric of claim
 34. 36. The laminate of claim 35, further comprising at least one layer of a metal foil on a surface of the at least one layer of the fabric.
 37. The laminate of claim 36, wherein the metal foil is a copper foil.
 38. A circuit board for use in an electronic product, comprising the fabric of claim
 34. 39. A method, comprising: impregnating a woven or non-woven fabric with the composition of claim 20 to form a pre-preg product.
 40. The method of claim 39, further comprising curing the curable composition to form a laminated product.
 41. The method of claim 40, wherein the method comprises curing the curable composition at a temperature between about 150° C. and about 250° C. 